Triazinyl-antraquinone dyes

ABSTRACT

A dye, which is suitable for dyeing cellulosic fiber materials, of the formula, ##STR1## wherein R and R&#39; are each hydrogen, a C 1  -C 4  alkyl, or C 1  -C 4  hydroxyalkyl, m is an integer of 1 to 6, n and n&#39; are each an integer of 2 to 4, and when m is 2 or more, n may be the same or different integer between 2 and 4, X is hydrogen or a group of the formula ##STR2## (wherein Q is a dye residue, R 1  is hydrogen or a C 1  -C 4  alkyl and R 2  is halogen); Y is hydrogen or a group of the formula ##STR3## (wherein Q&#39; is a dye residue, and when m is 2 or more, Q&#39;s may be the same or different, R 1  &#39; is hydrogen or a C 1  -C 4  alkyl and R 2  &#39; is halogen); Z is hydrogen or a group of the formula ##STR4## (wherein Q&#34; is a dye residue, R 1  &#34; is hydrogen or a C 1  -C 4  alkyl and R 2  &#34; is halogen, Q, Q&#39; and Q&#34; may independently be the same or different and X, Y and Z are not hydrogen at the same time).

This is a division of application Ser. No. 788,444 filed Apr. 18, 1977now U.S. Pat. No. 4,148,790, which in turn is a divisional ofapplication Ser. No. 471,986 filed May 21, 1974 (now U.S. Pat. No.4,038,267).

The present invention relates to a new reactive dye, preparation thereofand dyeing method including use of the dye.

In the field of dyeing and printing lately, an environmental pollutionhas also attracted great interest as in other fields, and particularlydecoloration of dyeing waste water has become a serious problem. Therehas been developed many decoloration techniques of dyeing waste water,however it is obvious that a basic solution to this problem is todevelop a dye and dyeing method free from the waste water problem.

Particularly in dyeing of cellulosic fiber materials using theconventional reactive dyes, the decoloration is very difficult, becausethe dyes are hydrolyzed in the course of dyeing and go into waste waterin a large amount without being fixed to the materials to be dyed. Thedifficulty, however, can be solved by an increase in fixing ratio of dyeto the materials, which also directly leads to cost reduction in dyeing.

The present inventors, as a result of the study based on the situationabove mentioned, have discovered a new reactive dye which has anextremely high fixing ratio compared with the conventional reactivedyes, thus having a much smaller proportion of the unreacted andhydrolyzed portions discharged into the dyeing waste water. The presentinventors, furthermore, have discovered that the new dyes can give anexcellent colour depth compared with the conventional reactive dyes.

The new reactive dyes of the present invention can be represented by thefollowing general formula (I), ##STR5## wherein R and R' are eachhydrogen, a C₁ -C₄ alkyl, or C₁ -C₄ hydroxyalkyl, m is an integer of 1to 6, n and n' are each an integer of 2 to 4, and when m is 2 or more, nmay be the same or different integer between 2 and 4, X is hydrogen or agroup of the formula ##STR6## (wherein Q is a dye residue, R₁ ishydrogen or a C₁ -C₄ alkyl and R₂ is halogen); Y is hydrogen or a groupof the formula ##STR7## (wherein Q' is a dye residue, and when m is 2 ormore, Q's may be the same or different, R₁ ' is hydrogen or a C₁ -C₄alkyl and R₂ ' is halogen); Z is hydrogen or a group of the formula##STR8## (wherein Q" is a dye residue, R₁ " is hydrogen or a C₁ -C₄alkyl and R₂ " is halogen, Q, Q' and Q" may independently be the same ordifferent and X, Y and Z are not hydrogen at the same time.).

In the present invention, the dye residue represented by Q, Q' or Q" isa residue of the general formula represented by the following free acidforms; ##STR9## wherein D is a diazo-component of benzene or naphthaleneseries which may contain an azo group, and a is 1 or 2, ##STR10##wherein D' is a diazo-component of benzene or naphthalene series whichmay contain an azo group, and b is 0 or 1, ##STR11## wherein D" is adiazo-component of benzene or naphthalene series which may contain anazo group, E is hydrogen, a halogen, methyl, methoxy or ethoxy, and F ishydrogen, methyl, methoxy, ethoxy or a group of the formula ##STR12## inwhich R₃ is hydrogen or a C₁ -C₄ alkyl, and G is a C₂ -C₅ aliphaticacyl, C₁ -C₄ alkylsulfonyl or carbamoyl, ##STR13## wherein J is acoupling-component of benzene, naphthalene or pyrazolone series, and dis 0, 1 or 2, ##STR14## wherein Me is a metallic atom of copper,chromium or cobalt, K and M are each hydrogen, a halogen, methyl,methoxy, ethoxy, carboxyl, sulfo or aryl azo group, and e is 1 or 2,##STR15## wherein Me and e are the same as defined above, f is aninteger of 1 to 3, ##STR16## wherein Me and e are the same as definedabove, T is hydrogen, a halogen or nitro, and g is 0, 1 or 2, ##STR17##wherein L is methyl, carboxyl, a C₂ -C₅ carboalkoxy or carbamide, P is ahalogen, methyl, sulfonic acid or sulfonamide, and h, k and j are each0, 1 or 2, ##STR18## wherein R₄ is hydrogen or a C₁ -C₄ alkyl, V is ahalogen or methyl, l and q are each 0, 1 or 2 and s is 0, 1, or 3,##STR19## wherein Pc is phthalocyanine which may be substituted with ahalogen, R₅ and R₆ are each hydrogen or a C₁ -C₄ alkyl, W is phenylenewhich may be substituted or a C₂ -C₄ alkylene, t is 1, 2 or 3, u is 0, 1or 2, and w is 1 or 2; and t, u and w are related to one another by thefollowing equation, ##STR20## wherein J' is a coupling component ofpyrazolone series, and d is the same as defined above, and ##STR21##wherein D'" is a diazo component of benzene and naphthalene series, andK and e are same as defined above.

The new reactive dyes of the present invention can be prepared by thefollowing processes, that is, by reacting2,4,6-trihalogeno-1,3,5-triazine, with an amine represented by theformula (II), ##STR22## wherein R, R', m, n and n' are the same asdefined above, and at least one dye of the formula (III), (IV) or (V),which dye has an amino group which can be acylated, ##STR23## (wherein Qand R₁ are the same as defined above,) ##STR24## (wherein Q' and R₁ 'are the same as defined above,) ##STR25## (wherein Q" and R₁ " are thesame as defined above,) in arbitrary order.

More specifically, the new reactive dyes of the present invention can beobtained by condensing a cyanuric halide, at 0° to 10° C. preferably inan aqueous medium, with at least one dye of the formula represented by afree acid form, ##STR26## wherein R" is hydrogen, a C₁ -C₄ alkyl or C₁-C₄ hydroxyalkyl, D and a are the same as defined above, ##STR27##wherein R", D' and b are the same as defined above, ##STR28## whereinR", D", E and F are the same as defined above, ##STR29## wherein R", Jand d are same as defined above, ##STR30## wherein R", K, M, Me and eare the same as defined above, ##STR31## wherein R", Me, e and f are thesame as defined above, ##STR32## wherein R", Me T, e and g are the sameas defined above, ##STR33## wherein R", L, P, h, k and j are the same asdefined above, ##STR34## wherein R", R₄, V, l, q and s are the same asdefined above, ##STR35## wherein R", Pc, R₅, R₆, W, t, u and w are thesame as defined above, and then further condensing the resultingcompounds, at 20° to 60° C. preferably in an aqueous medium and in arange of pH between 3 and 7, with 1/m+2˜1 by molar ratio of the aminerepresented by the formula (II).

Alternatively, the new reactive dyes of the present invention can beobtained by first condensing cyanuric halide with 1/m+2˜1 by molar ratioof the amine of the formula (II) at 0° to 5° C., preferably in anaqueous medium and in the range of pH between 3 and 7, and thencondensing the resulting compounds, at 20° to 60° C. preferably in anaqueous medium, with at least one dye of the formula (III), (IV) or (V)preferably with dyes represented by the formulas (2) to (11).

For particularly brilliant green dyes, it is particularly preferred tocombine the dyes of the general formula (13), ##STR36## wherein J' is acoupling--component residue of pyrazolone series, and R" and d are thesame as defined above, with the dyes of the general formula (11).

In addition, for preparing black dyes, it is particularly preferred tocombine a mixture of the dye of the formula (14), ##STR37## wherein D"'is a diazo--component residue of benzene or naphthalene series, and K, eand R" are the same as defined above, and the aforesaid dye (2), withthe aforesaid dye (4) or (13).

The reactive dye of the formula (I) can also be prepared by reacting theamine represented by the formula (II), with at least one compound of thegeneral formula, ##STR38## wherein Q, R₁ and R₂ are the same as definedabove, ##STR39## wherein Q', R₁ ' and R₂ ' are the same as definedabove, ##STR40## wherein Q", R₁ " and R₂ " are the same as definedabove.

The dye of the formula (I) in which Q, Q' and Q" are each an azoic dyeresidue can be prepared by diazotising a compound of the generalformula, ##STR41## wherein R, R', m, n and n' are the same as definedabove, X' is hydrogen, or a group of the formula ##STR42## in which R₁and R₂ are the same as defined above, and a and d are the same asdefined above, Y' is hydrogen, or a group of the formula ##STR43## inwhich R₁ ' and R₂ ' are the same as defined above, a' is 1 or 2 and d'is 0, 1 or 2, and Z' is hydrogen or a group of the formula ##STR44## inwhich R₁ " and R₂ " are the same as defined above, a" is 1 or 2 and d"is 0, 1 or 2, and then by coupling the resulting diazotised compoundwith a coupling component of the gene 1 formula,

    J--H

wherein J is the same as defined above.

Moreover, the dye of the formula (I) in which Q, Q' and Q" are each anazoic dye residue can be prepared by coupling a compound of the generalformula, ##STR45## wherein R, m, n and n' are the same as defined above,X" is hydrogen or a group of the formula ##STR46## in which R₁, R₂ and aare the same as defined above, Y" is hydrogen or a group of the formula##STR47## in which R₁ ', R₂ ' and a' are the same as defined above, andZ" is hydrogen or a group of the formula ##STR48## in which R₁ ", R₂ "and a" are the same as defined above, with the diazotized product of theamine represented by the formula,

    D--NH.sub.2

wherein D is same as defined above.

More concretely speaking, when aimed dyes are azoic dyes ormetal-containing azoic dyes which have a fiber-reactive group in adiazo-component, they can also be prepared by the following process,that is, by the process including first condensing cyanuric halide, at0° to 10° C. preferably in an aqueous medium, with a compound of theformula represented by a free acid form, ##STR49## wherein d and R" arethe same as defined above, and R"' is hydrogen, a C₂ -C₅ aliphatic acyl,aromatic of benzene series acyl or C₁ -C₄ alkylsulfonyl, or a compoundof the formula represented by a free acid form, ##STR50## wherein a, R"and R"' are the same as defined above, and a relative position of --NHR"and --NH--R"' groups on a naphthalene nucleus is 1-4, 1-5 or 2-6,condensing the resulting compounds with 1/m+2˜1 by molar ratio of theamine (II) at 20° to 60° C. preferably in an aqueous medium and in arange of pH between 3 and 7, and then, if necessary, hydrolyzing an acylgroup by a well-known method followed by diazotization and coupling.

Alternatively, the aimed dye can be prepared by first condensingcyanuric halide with 1/m+2˜1 by molar ratio of an amine of the formula(II) at 0° to 5° C. preferably in an aqueous medium and in a range of pHbetween 3 and 7, condensing the resulting compound with the compound ofthe formula (15) or (16) at 20° to 60° C. preferably in an aqueousmedium, and then, if necessary, hydrolyzing an acyl group by awell-known method followed by diazotization and coupling.

When the aimed dyes are azoic dyes or metal-containing azoic dyes whichhave a fiber-reactive group in a coupling-component, the dyes can beprepared by first condensing cyanuric halide with a compounds of theformula (17) represented by a free acid form, ##STR51## wherein a and R"are same as defined above, at 0° to 10° C. preferably in an aqueousmedium, condensing the resulting compound with 1/m+2˜1 by molar ratio ofan amine of the formula (II) at 20° to 60° C. preferably in an aqueousmedium and in a range of pH between 3 and 7, and then coupling with adiazo-component by a well-known method.

Alternatively, the aimed dyes can be prepared by first condensingcyanuric halide with 1/m+2˜1 by molar ratio of an amine of the formula(II) at 0° to 5° C. preferably in an aqueous medium and in a range of pHbetween 3 and 7, condensing the resulting compound with a compound ofthe formula (17) at 20° to 60° C., and then coupling with adiazo-component by a well-known method.

With part of metal-containing azoic dyes, aimed dyes can be obtained byfirst preparing metal-free dyes according to the processes abovementioned and then carrying out an oxidative metallizing treatment.

The amine represented by the formula (II) include diethylenetriamine,dipropylenetriamine, triethylenetetramine,mono-N-(β-aminoethyl)-dipropylenetriamine, tetraethylenepentamine,pentaethylenehexamine, hexaethyleneheptamine,N,N'-dimethyldiethylenetriamine,N,N'-bis(γ-aminopropyl)-butylenediamine,mono-N-(β-hydroxyethyl)-diethylenetriamine and so forth. The cyanurichalide used in the present invention includes cyanuric chloride andcyanuric bromide.

Coloration of cellulosic textile materials with the present dyes of theformula (I) alone or combination thereof can be carried out by dyeing orprinting the materials in the presence of an acid-binding agent, thusgiving deep dyeings.

For this purpose, the following methods are often used.

The first is the so-called dip dyeing process including impregnating thefiber materials in a dilute aqueous medium containing an acid-bindingagent and a dye. In this case the agent can be added before or after orat the same time with the addition of dye.

The second is a padding process including treating the fiber materialswith an acid-binding agent in an aqueous medium before or after or atthe same time with impregnating of the materials with a dye liquor. Inaddition, another method is a printing process in which the fibermaterials are printed with a printing paste containing a dye and anacid-binding agent, or the materials are treated with an aqueousacid-binding agent solution before or after printing with adye-containing printing paste.

The acid-binding agents used for the various dyeing or printingprocesses include caustic alkali such as caustic soda and causticpotash, magnesium oxide, and alkali metal salts of weak acid such aspotassium carbonate, sodium carbonate, sodium bicarbonate, potassiumbicarbonate, trisodium phosphate and sodium silicate.

In coloration of textile materials by a dipping process, the amount ofacid-binding agent used is advantageously 0.1 to 0.3% based on the totalamount when caustic alkalis are used, and 1.0 to 5% based on the totalamount when alkali metal salts are used. And the coloration is carriedout by keeping the materials in an aqueous dilute medium containing adye and such the acid-binding agent at above 50° C. preferably at from70° C. to a boiling point of the solution, for a definite period oftime, and then rinsing followed by soaping in a dilute detergentsolution, rinsing and drying.

In this case, the acid-binding agent may be added after the dye liquorcontaining the textile materials and the dye has been heated to above50° C., more preferably to from 70° C. to a boiling point of the liquor.

The dye liquor may advantageously contain other electrolytes, forexample alkali metal salts such as sodium sulfate and sodium chloride,in order to accelerate the exhaustion of dye liquor.

For the padding process of the textile materials, the coloration can beachieved by padding the materials through a dye liquor containing anacid-binding agent, fixing the dye by a short-period steaming or byaging at room temperature, and the rinsing and drying. Alternatively,the materials, after padded through the dye liquor and then dried, maybe impregnated in a cooled solution containing the acid-binding agent,immediately steamed under a saturated steam of 95° to 102° C. followedby steaming under an oven-heated steam of 95° to 102° C., or 140° to160° C.

The aqueous medium in which a dye is applied to textile materials maycontain other materials such as sodium sulfate, sodium chloride, sodiumalginate, water-soluble alkyl ethers of cellulose and urea.

For the treatment of impregnated textile materials with an acid-bindingagent in an aqueous medium, the materials after drying are dipped in anacid-binding agent solution at, particularly, a temperature between roomtemperature and a boiling point of the solution. The dipping time varieswith the treating conditions and dyes used, however a period of about 1minute is generally sufficient when caustic alkali is used at about 100°C. The materials, after treated in the acid-binding agent solution, arerinsed, treated with a dilute solution of as weak acid as possible, forexample a dilute acetic acid solution, to neutralize the remainingacid-binding agent, rinsed again and dried.

The aqueous solution of acid-binding agent may advantageously containother materials, particularly electrolytes for example alkali metalsalts such as sodium sulfate and sodium chloride, however theacid-binding agent itself is suitably a caustic alkali solutioncontaining sodium chloride in a large amount.

Superiority in the fixing ratio of the dyes of the present inventionover the conventional monochlorotriazine type reactive dyes will beshown in the following table.

    ______________________________________                                                                     Fixing ratio.sup.1                                                Dyeing      (unmercerized                                    Dye used         concentration                                                                             cotton yarn)                                     ______________________________________                                        Present dye (I)  4% o.w.f.   85.6%                                            Well-known dye (VI)                                                                            "           43.3%                                            Present dye (II) "           80.5%                                            Well-known dye (VII)                                                                           "           50.3%                                            Present dye (III)                                                                              "           67.0%                                            Well-known dye (VIII)                                                                          "           45.2%                                            Present dye (IV) "           70.6%                                            Well-known dye (IX)                                                                            "           39.8%                                            Present dye (V)  "           68.0%                                            Well-known dye (X)                                                                             "           46.6%                                            ______________________________________                                         Note.sup. 1 :                                                                 ##STR52##                                                                

(The dye and the dye fixed on the yarn were respectively dissolved in80% H₂ SO₄, and each solution was measured by an absorptiometricmethod.) The structural components of the present dyes mentioned abovear as follows. ##STR53##? (I)?

(1 mole), diethylenetriamine (1/3 mole) ##STR54##

(1 mole), diethylenetriamine (1/3 mole) ##STR55##

(1 mole), diethylenetriamine (1/2 mole) ##STR56##

(1 mole), diethylenetriamine (1/2 mole) ##STR57##

(1 mole), diethylenetriamine (1/2 mole) The well-known dyes as areference are described in the following patents. ##STR58##Corresponding to I; the compound No. 6 described in the table attachedto Example 5 in German Patent Specification No. 1,101,657. ##STR59##Corresponding to II; described in German Pat. No. 1,101,657. ##STR60##Corresponding to III; the compound No. 13 described in the Table 1attached to Example 2 in British Patent Specification No. 869,279.##STR61## Corresponding to IV; the compound described in Example 2 inBritish Patent Specification No. 899,376. ##STR62## Corresponding to V;the compound No. 17 described in the table attached to Example 3 inGerman Patent Specification No. 1,156,914.

As shown in the above table, the dyes of the present invention can beapplied to any cellulosic textile materials, for example cotton, hempand regenerated cellulose, and show an extremely high fixing ratioparticularly by a dipping process and a padding process, thus being ofvery high industrial value.

The present invention will be illustrated with reference to thefollowing examples, which are only given for the purpose ofillustration, and not to be interpreted as limiting.

EXAMPLE 1

100 parts of bleached cotton yarn was dyed at 75° C. for 1 hour in 3000parts of a dye liquor containing 150 parts of sodium sulfate, 9 parts oftrisodium phosphate and 4 parts of the dye which had been prepared bycondensing 6-(4", 6"-dichlorotriazine-2"-yl)amino-2-(2'-sulfophenylazo)-1-naphthol-3-sulfonic acid with 1/3 by molarratio of diethylenetriamine under the condition as described in Example2. Thereafter the dyed yarn was taken out, rinsed in warm water, boiledfor 5 minutes, rinsed in a 0.2% aqueous detergent solution and finallydried.

Thus, the yarn was dyed in a deep orange shade which was very fast towashing and sunlight.

EXAMPLE 2

The dye which was used in Example 1 was obtained as follows. The diazocompound obtained from 16.5 parts of aniline-2-sulfonic acid was coupledwith the primary condensation product obtained from 18.5 parts ofcyanuric chloride and 26.1 parts of sodium6-amino-1-naphthol-3-sulfonate. After the coupling reaction wascompleted, the reaction solution was adjusted to about 7 of pH and thena solution of 3.5 parts of diethylenetriamine in 50 parts of water wasadded to the solution which was then heated to 40° to 45° C. and stirredat the same temperature for 3 hours. After the condensation reaction wascompleted, the solution was adjusted to about 6.5 of pH, salted out withsodium choride, filtered and dried. In this example, replacement of 3.5parts of diethylenetriamine by 3.6 parts of triethylentetramine and 3.8parts of tetraethylenepentamine could give similar dyes, respectively.

EXAMPLE 3

100 parts of bleached cotton yarn was dyed at 85° C. for 1 hour in 3000parts of a dye liquor containing 150 parts of sodium chloride, 15 partsof sodium carbonate and 2 parts of the dye which had been prepared bycondensing1-amino-4-[4'-(4",6"-dichlorotriazin-2"-yl)amino-anilino]-anthraquinone-2,3'-disulfonicacid with 1/3 by molar ratio of diethylenetriamine under the conditionas described in Example 4. Thereafter the dyed yarn was rinsed as inExample 1. Thus, the yarn was dyed in a deep blue shade which was veryfast to washing and sunlight.

EXAMPLE 4

The dye which was used in Example 3 was prepared as follows.

A solution of 18.5 parts of cyanuric chloride in 100 parts of acetonewas poured into 500 parts of ice water to obtain an aqueous suspensionof cyanuric chloride. To the suspension was added, at below 5° C. over30 minutes, a solution of 53.3 parts of disodium1-amino-4-(4'-aminoanilino)-anthraquinone-2,3'-disulfonate in 800 partsof water which was made slightly alkaline with sodium carbonate. Thereaction mixture was further stirred for about 2 hours at 6 to 7 of pHto complete the condensation reaction. Then a solution of 3.5 parts ofdiethylenetramine in 50 parts of water was added to the solution whichwas then kept at 40° to 45° C. for 2.5 hours while stirring. Then thesolution was salted out with sodium chloride, filtered and dried.

A similar dye was also obtained even by condensing cyanuric chloridewith, at first, diethylenetriamine and then the anthraquinone dye.

EXAMPLE 5

100 parts of bleached cotton yarn was dyed at 85° C. for 1 hour in 3000parts of a dye liquor containing 150 parts of anhydrous sodium sulfate,15 parts of sodium carbonate and 1 part of the dye which had beenobtained by condensing a 1:1 copper complex of6-amino-2-[4'-(2",5"-disulfophenylazo)-2'-oxy-5'-methylphenylazo]-1-naphthol-3-sulfonicacid with cyanuric chloride and diethylenetriamine in this order underthe condition as described in Example 6. Thereafter the dyed yarn wastaken out, rinsed in warm water, boiled for 5 minutes, rinsed in a 0.2%aqueous detergent solution and finally dried.

Thus, the yarn was dyed in a deep blue shade which was fast to washingand sunlight.

EXAMPLE 6

The dye which was used in Example 5 was obtained as follows.

The diazo compound obtained from aniline-2,5-disulfonic acid was coupledwith 1-amino-2-methoxy-5-methylbenzene to give the aminomonoazocompound. The resulting compound was further diazotized and coupled with6-amino-1-naphthol-3-sulfonic acid under an alkaline condition. Theaminodisazo dye thus obtained was converted into a copper complex byheating at 95° to 100° C. for 20 hours in a solution of copper sulfatein aqueous ammonia. 76.4 parts of trisodium salt of the resultingcomplex was dissolved in 1000 parts of water and added at 0° to 5° C. toa cyanuric chloride suspension which had been prepared by pouring asolution of 18.5 parts of cyanuric chloride in 100 parts of acetone into500 parts of ice water. The resulting mixture was raised to 6.5 to 7.0of pH with a sodium carbonate solution and maintained in this rangewhile stirring by further adding the solution until pH change was nolonger observed. Thereafter a solution of 3.5 parts ofdiethylenetriamine in 50 parts of water was added to the reactionsolution which was then heated to 40° to 45° C. and maintained for about2 hours while stirring. The solution was adjusted to near 6.5 of pH,salted out with sodium chloride, filtered and dried at 40° to 50° C.

EXAMPLE 7

100 parts of a uniform printing paste was prepared by dissolving 2 partsof the dye used in Example 1 and 10 parts of urea in 30 parts of hotwater and then adding thereto 55 parts of a 4% paste of sodium alginate(a medium-viscosity grade) and 3 parts of sodium bicarbonate.

Cotton broad cloth was printed with this printing color paste, dried andthen steamed at 100° C. for 10 minutes followed by rinsing and soapingfor finishing.

The printed fabric thus obtained was dyed in a deep orange shade whichwas highly fast to washing and sunlight.

EXAMPLE 8

Deep dyeings of excellent fastness were obtained using the dyes shown inthe following table in the same manner as described in Examples 1, 3, 5and 7. In the table, the shades on cellulosic textile materials areshown in the fouth column that were obtained with the dyes which hadbeen prepared by condensing the dyes in the first column, halogenatedtriazines in the second column and compounds (polyamines) in the thirdcolumn.

    __________________________________________________________________________                               Halogenat-                                         No.                                                                              Dyestuff                ed triazine                                                                         Polyamine   Shade                            __________________________________________________________________________    1  6-Amino-2-(4'-methylphenylazo)-1-naphthol-                                                            Cyanuric                                                                            Dipropylene triamine                                                                      Reddish                             2',3-sulfonic acid      chloride          orange                           2  6-Amino-2-(4'-methylphenylazo)-1-naphthol-                                                            Cyanuric                                                                            Triethylene tetramine                                                                     Reddish                             2',3-sulfonic acid"     chloride          orange                           3  6-Amino-2-(4'-methylphenylazo)-1-naphthol-                                                            Cyanuric                                                                            Tetraethylene pentamine                                                                   Reddish                             2',3-sulfonic acid"     chloride          orange                           4  6-Amino-2-(4'-methylphenylazo)-1-naphthol-                                                            Cyanuric                                                                            Pentaethylene hexamine                                                                    Reddish                             2',3-sulfonic acid      chloride          orange                           5  6-Amino-2-(4'-methylphenylazo)-1-naphthol-                                                            Cyanuric                                                                            Hexaethylene heptamine                                                                    Reddish                             2',3-sulfonic acid      chloride          orange                           6  6-Amino-2-(4'-chlorophenylazo)-1-naphthol-                                                            Cyanuric                                                                            Diethylene triamine                                                                       Orange                              2',3-disulfonic acid    bromide                                            7  6-Amino-2-(4'-chloro-5'-methylphenylazo)-                                                             Cyanuric                                                                            "           "                                   1-naphthol-2',3-disulfonic acid                                                                       chloride                                           8  4-Amino-2-acethylamino-1-(1',5'-disulfo-                                                              Cyanuric                                                                            Tetraethylene pentamine                                                                   Yellow                              naphthyl-2'-azo)-benzene                                                                              chloride                                           9  4-(4',8'-disulfonaphthyl-2'-azo)-3-methyl-                                                            Cyanuric                                                                            Dipropylene triamine                                                                      "                                   aniline                 chloride                                           10 4-(4',8'-disulfonaphthyl-2'-azo)-2-methoxy-                                                           Cyanuric                                                                            "           Reddish                             5-methylaniline         chloride          yellow                           11 4-(3',6',8'-trisulfonaphthyl-2'-azo)-3-                                                               Cyanuric                                                                            Dipropylene triamine                                                                      Reddish                             ureidoaniline           chloride          yellow                           12 8-Amino-2-(2'-carboxyphenylazo)-1-naphthol-                                                           Cyanuric                                                                            Triethylene tetramine                                                                     Red                                 3,6-disulfonic acid     chloride                                           13 4-(4"-Amino-2"-sulfophenylazo)-1-(2'-methyl-                                                          Cyanuric                                                                            Diethylene triamine                                                                       Yellow                              5'-sulfophenyl)-3-methyl-5-pyrazolone                                                                 chloride                                           14 4-(5"-Amino-2"-sulfophenylazo)-1-(2',5' -                                                             Cyanuric                                                                            "           Greenish                            dichloro-4'-sulfophenyl)-3-methyl-5-pyrazolone                                                        chloride          yellow                           15 4-(5"-Amino-2"-sulfophenylazo)-1-(4'-sulfo-                                                           Cyanuric                                                                            "           Yellow                              phenyl)-3-methyl-5-pyrazolone                                                                         chloride                                           16 4-(5"-Amino-2"-sulfophenylazo)-1-(4'-sulfo-                                                           Cyanuric                                                                            Pentaethylene hexamine                                                                    Reddish                             phenyl)-3-carboxy-5-pyrazolone                                                                        chloride          yellow                           17 4-(5"-Amino-2"-sulfophenylazo)-1-(4'-methoxy-                                                         Cyanuric                                                                            Triethylene tetramine                                                                     Greenish                            2'-sulfophenyl)-3-methyl-5-pyrazolone                                                                 chloride          yellow                           18 8-Amino-7-(4-methoxyphenylazo)-1-naphthol-3,6-                                                        Cyanuric                                                                            "           Red                                 disulfonic acid         chloride                                           19 8-Methylamino-7-(2'-sulfophenylazo)-1-                                                                Cyanuric                                                                            Tetraethylene pentamine                                                                   Red                                 naphthol-3,6-disulfonic acid                                                                          bromide                                            20 8-Amino-2,7-bis(5'-amino-2'-sulfophenylazo)-                                                          Cyanuric                                                                            "           Greenish                            1-naphthol-3,6-disulfonic acid                                                                        chloride          blue                             21 8-Amino-2,7-bis(4'-amino-2'-sulfophenylazo)-                                                          Cyanuric                                                                            Diethylene triamine                                                                       Dark                                1-naphthol-3,6-disulfonic acid                                                                        chloride          green                            22 1,3-Dihydroxy-2-(2'-sulfo-4'-aminophenylazo)-                                                         Cyanuric                                                                            "           Brown                               4-(2"-hydroxy-5"-sulfophenylazo)-benzene                                                              chloride                                           23 1,3-Dihydroxy-2-(4"-amino-2',2"-disulfo-                                                              Cyanuric                                                                            "           "                                   stilbene-4'-ylazo)-4-(2"-hydroxy-5"-                                                                  chloride                                              sulfophenylazo)-benzene                                                    24 1-Amino-4-[4'-(2",5",7"-trisulfonaphthyl-                                                             Cyanuric                                                                            Hexaethylene heptamine                                                                    "                                   1"-azo)-2',5'-dimethylphenylazo]-                                                                     chloride                                              naphthalene-6-sulfonic acid                                                25 6-N-butylamino-2-[4'-(2"-sulfophenylazo)-2'-                                                          Cyanuric                                                                            Pentaethylene hexamine                                                                    Blue                                hydroxy-5'-methylphenylazo]-1-naphthol-3-                                                             chloride                                              sulfonic acid                                                              26 1-(2'-Methyl-3'-amino-5'-sulfophenyl)-3-                                                              Cyanuric                                                                            Diethylene triamine                                                                       Red                                 carboxy-4-[4"-(2"-sulfophenylazo)-2"-                                                                 chloride                                              methoxy-5"-methylphenylazo]-5-pyrazolone                                   27 1-Amino-4-(4'-methylaminoanilino)-                                                                    Cyanuric                                                                            Tetraethylene pentamine                                                                   Blue                                anthraquinone-2-sulfonic acid                                                                         chloride                                           28 1-Amino-4-(3'-β-hydroxyethylaminoanilino)-                                                       Cyanuric                                                                            "           "                                   anthraquinone-2,5-disulfonic acid                                                                     chloride                                           29 1-Amino-4-(4'-n-butylaminoanilino)-                                                                   Cyanuric                                                                            Diethylene triamine                                                                       Reddish                             anthraquinone-2,3'-disulfonic acid                                                                    chloride          blue                             30 1-Amino-4-[4'-(4"-aminophenylazo)-anilino]-                                                           Cyanuric                                                                            "           Olive                               anthraquinone-2,2',5-trisulfonic acid                                                                 chloride          green                            31 1-Amino-4-(4'-aminoanilino)-anthraquinone-                                                            Cyanuric                                                                            "           Greenish                            2,3',6-trisulfonic acid chloride          blue                             32 1-Amino-4-(4'-amino-3'-carboxyanilino)-                                                               Cyanuric                                                                            Triethylene tetramine                                                                     Greenish                            anthraquinone-2,5-disulfonic acid                                                                     chloride          blue                             33 1-Amino-4-(3'-aminoanilino)-anthraquinone-                                                            Cyanuric                                                                            Diethylene triamine                                                                       Blue                                2,4',5-trisulfonic acid chloride                                           34 1-Amino-4-[4'-(4"-aminophenyl)-anilino]-                                                              Cyanuric                                                                            Diethylene triamine                                                                       Greenish                            anthraquinone-2,3",5-trisulfonic acid                                                                 chloride          blue                             35 1-Amino-4-(4'-methylaminoanilino)-                                                                    Cyanuric                                                                            Pentaethylene hexamine                                                                    Reddish                             anthraquinone-2,3',5-trisulfonic acid                                                                 chloride          blue                             36 1-Amino-4-(4'-ethylaminoanilino)-                                                                     Cyanuric                                                                            "           Reddish                             anthraquinone-2,3'-disulfonic acid                                                                    chloride          blue                             37 1-Amino-4-(3'-amino-6'-methylanilino)-                                                                Cyanuric                                                                            Diethylene triamine                                                                       Reddish                             anthraquinone-2,4'-disulfonic acid                                                                    chloride          blue                             38 1-Amino-4-(3'-aminoanilino)-anthraquinone-                                                            Cyanuric                                                                            "           Reddish                             2,4'-disulfonic acid    bromide           blue                             39 1-Amino-4-(4'-aminoanilino)-anthraquinone-                                                            Cyanuric                                                                            Triethylene tetramine                                                                     Greenish                            2,3',5-trisulfonic acid bromide           blue                             40 1-Amino-4-(3'-aminoanilino)-anthraquinone-                                                            Cyanuric                                                                            "           Blue                                2,4',6'-trisulfonic acid                                                                              bromide                                            41 1-Amino-4-(3'-amino-2',4',6'-trimethyl-                                                               Cyanuric                                                                            "           Reddish                             anilino)-anthraquinone-2,5'-disulfonic acid                                                           chloride          blue                             42 1:1 Copper complex of 6-amino-2-(2'-                                                                  Cyanuric                                                                            Diethylene triamine                                                                       Violet                              hydroxy-3',5'-disulfophenylazo)-1-naphthol-                                                           chloride                                              3-sulfonic acid                                                            43 1:2 Chromium complex of 6-amino-2-(2'-                                                                Cyanuric                                                                            "           Reddish                             carboxyphenylazo)-1-naphthol-3-sulfonic acid                                                          chloride          brown                            44 1:2 Cobalt complex of 6-amino-2-(2'-hydroxy-                                                          Cyanuric                                                                            "           Brown                               3'-sulfo-5'-nitrophenylazo)-1-naphthol-3-                                                             chloride                                              sulfonic acid                                                              45 Nickel complex of 6-amino-2-[4'-(2",5"-                                                               Cyanuric                                                                            "           Blue                                disulfophenylazo)-2'-hydroxy-5'-methyl-                                                               chloride                                              phenylazo]-1-naphthol-3-sulfonic acid                                      46 1:1 Copper complex of 8-amino-2-[4-(2",5"-                                                            Cyanuric                                                                            Tetraethylene pentamine                                                                   "                                   disulfophenylazo)-2'-oxy-5'-methylphenylazo]-                                                         chloride                                              1-naphthol-3,6-disulfonic acid                                             47 1:2 Cobalt complex of 6-amino-2-(2'-hydroxy-                                                          Cyanuric                                                                            "           Violet                              4'-sulfo-6'-nitronaphthyl-1'-azo)-1-naphthol-                                                         chloride          brown                               3-sulfonic acid                                                            48 1:2 Chromium complex of the above compound                                                            Cyanuric                                                                            Tetraethylene pentamine                                                                   Greenish                                                    chloride          grey                             49 1:1 Copper complex of 6-amino-2-(2'-                                                                  Cyanuric                                                                            Diethylene triamine                                                                       Ruby                                hydroxy-5'-sulfophenylazo)-1-naphthol-3,                                                              chloride                                              5-disulfonic acid                                                          50 1:1 Copper complex of 6-amino-2-[4'-(4"-                                                              Cyanuric                                                                            "           Navy                                sulfophenylazo)-2'-hydroxy-5'-methyl-                                                                 chloride                                              phenylazo]-1-naphthol-3-sulfonic acid                                      51 1:1 Copper complex of 8-amino-2-[4'-(3",6",                                                           Cyanuric                                                                            "           Blue                                8"-trisulfonaphthyl-2"-azo)-2'-hydroxy-5'-                                                            chloride                                              methylphenylazo]-1-naphthol-3,6-disulfonic                                    acid                                                                       52 1:1 Copper complex of 8-amino-2-[4'-(6",8"-                                                           Cyanuric                                                                            Triethylene tetramine                                                                     Violet                              disulfonaphthyl-2"-azo)-2'-carboxyphenylazo]-                                                         chloride                                              1-naphthol-3,6-disulfonic acid                                             __________________________________________________________________________

EXAMPLE 9

100 parts of cotton fabric was added to a dye liquor containing 80 partsof sodium chloride, 80 parts of trisodium phosphate and 2 parts ofmonochlorotriazinyl phthalocyanine dye obtained in Example 10. Then theliquor was heated to 60° C. in 0.5 hour, and 80 parts of sodium chloridewas added to the liquor which was then heated to 80° C. in 15 minutesand maintained at this temperature for 0.5 hour. The dyeings thusobtained were rinsed and soaped in a boiling 0.3% aqueous nonionicdetergent solution for 15 minutes. The fabric was dyed in a very deepgreenish blue shade which was very fast to washing and sunlight.

EXAMPLE 10

The dye which was used in Example 9 was obtained as follows.

60 parts of copper phthalocyanine was added to 720 parts by volume ofchlorosulfonic acid, and the mixture was heated at 140° to 141° C. for 2hours, cooled and stirred into ice water. The precipitated sulfochloridewas filtered and washed thoroughly with ice water to obtain a wet cake.The wet cake of crude copper phthalocyanine sulfochloride thus obtainedwas slurried by thoroughly mixing with 300 parts of ice, and the mixturewas adjusted, at 0° to 3° C., to 6.5 of pH with a dilute caustic sodasolution. Into the slurry were rapidly stirred a solution of 15 parts of1-amino-4-acetylaminobenzene in 580 parts of acetone, and 50 parts byvolume of pyridine. The mixture was stirred at room temperature for 20hours, steam distilled under an alkaline state to remove pyridinecompletely, and then made acid to Congo Red with a dilute hydrochloricacid to precipitate the dye. The filtered dye wet cake was heated at100° C. for 1 hour in a solution of 50 to 60 parts of conc. sulfuricacid in 1250 parts of water and then filtered. The dye wet cake wasdissolved in 1000 parts of hot water containing a small amount ofalkali, and then the solution was steam distilled at 8.5 of pH until avolatile amine was no longer detected, made alkaline to Brilliant Yellowand salted out with sodium chloride to reprecipitate the dye. Theproduct thus obtained was considered to be a sodium salt of copperphthalocyanine monosulfonyl-N-(p-aminophenyl)-amide-trisulfonic acid.

The salt was dissolved in 2000 parts of water and adjusted exactly to7.0 of pH. The solution was condensed, at 0° to 4° C., with 18.5 partsof cyanuric chloride in a form of aqueous suspension which had beenprepared by pouring its acetone solution into ice, while keeping pH ofthe reaction solution at 5 to 7.5 with 1 N-aqueous caustic sodasolution. After the reaction, the solution was further reacted with anaqueous solution of 3.5 parts of diethylenetriamine at 40° to 45° C. for3 hours. Thereafter the solution was adjusted to about 6.5 of pH andsalted out to precipitate the desired dye.

Alternatively, a dye of the similar quality was obtained by firstcondensing cyanuric chloride with diethylenetriamine, and thencondensing the resulting compound with the above compound which wasconsidered to be copperphthalocyanine-monosulfonyl-N-(p-aminophenyl)-amide-trisulfonic acid.

EXAMPLE 11

When the dye which was used in Example 9 was replaced by 2 parts of thedye prepared by the following process, brilliant blue dyeings of goodfastness to washing and sunlight were obtained.

57.5 parts of copper phthalocyanine was added to 537 parts ofchlorosulfonic acid while stirring at a temperature of below about 30°C. Then the mixture was stirred at room temperature for 30 minutes,heated to from 130° to 133° C. over 1.5 hours and maintained at the sametemperature for 4 hours. After the reaction was completed, the reactionsolution was cooled and stirred into a mixture of 500 parts of water,280 parts of sodium chloride and 3000 parts of crushed ice. The mixedsolution was stirred for a short time, filtered and washed with amixture of 600 parts by volume of saturated sodium chloride solution and200 parts of ice to obtain crude copper phthalocyanine sulfochloride asan acidic wet cake. The sulfochloride was considered to be a mixture ofcopper phthalocyanine-3,3',3"-trisulfochloride-3'"-monosulfonic acid andcorresponding copper phthalocyanine-disulfochloridedisulfonic acid. Theacidic wet cake of crude sulfochloride was slurried by thoroughly mixingwith 300 parts of ice and adjusted, at 0° to 3° C., to 6.5 to 7.0 of pHwith a cold, dilute aqueous caustic soda solution. The neutralizedslurry was mixed with 5 parts of sodium carbonate and a solution of 14parts of 4-aminoformylaniline in 500 parts of water, then immediatelywith 15 parts of sodium carbonate. The mixture was stirred at 20° to 23°C. for 24 hours, and acidified with hydrochloric acid to precipitate adye acid which was then filtered. The filtered cake which was acidic toCongo Red was suspended in 1000 parts of water and hydrolyzed by adding60 parts of conc. sulfuric acid in a dilute solution so that the totalvolume did not exceed 1500 parts by volume, and by heating the whole at100° C. for 1 hour. After cooling, the mixture was filtered, and the wetcake was again suspended in water. The solution was made alkaline withan aqueous caustic soda solution, steam distilled to remove somevolatile amines, adjusted to 7.5 of pH and then salted out with sodiumchloride to obtain a dye.

The dye wet cake thus obtained was dissolved in 2000 parts of water, andthe solution was adjusted exactly to pH 7.0 and condensed, at 0° to 4°C., with 18.5 parts of cyanuric chloride in a form of aqueous suspensionwhich had been prepared by pouring its acetone solution into ice water.During the condensation the solution was kept at 5.0 to 7.5 of pH with 1N-aqueous caustic soda solution. After the reaction was completed, anaqueous solution containing 3.5 parts of diethylenetriamine was added tothe cold solution, and the mixture was heated to 40° to 45° C. and keptat the same temperature for 3 hours. After the second condensation wascompleted, the solution was adjusted to about 6.5 of pH and salted outto obtain the desired dye.

EXAMPLE 12

One part of the dye which was used in Example 9 was dissolved in 100parts of water. Cotton fabric was padded at 80° C. with the dye liquor,squeezed to 75% of pick-up on a padder and dried at room temperature.The dried fabric was then padded with a solution containing 10 g/l ofcaustic soda and 300 g/l of sodium chloride and squeezed to 75% ofpick-up. The fabric was steamed at 100° to 101° C. for 1 minute, rinsed,treated with a 0.5% sodium carbonate solution, soaped in a boiling 0.3%nonionic detergent solution for 15 minutes, rinsed and dried.

The cotton fabric was dyed in a greenish blue shade of good fastness towashing and sunlight.

EXAMPLE 13

In the same manner as described in Example 12, deep green dyeings ofgood fastness were obtained by using 1 part of the dye prepared by thefollowing process.

60 parts of copper phthalocyanine was added to 720 parts ofchlorosulfonic acid, and the mixture was heated at 140° to 141° C. for 2hours. Then the mixture was cooled and stirred into ice water toprecipitate sulfochloride which was then filtered and washed thoroughlywith ice water. Crude copper phthalocyanine sulfochloride thus obtainedwas slurried by thoroughly mixing with 300 parts of ice. The slurry wasadjusted, at 0° to 3° C., to 7.5 of pH with a dilute caustic sodasolution and then 30 parts of calcium carbonate and a solution of 21parts of sodium 1,4-diaminobenzene-3-sulfonate in 580 parts by volume ofwater were rapidly added thereto. The mixture was then stirred at roomtemperature for 20 to 24 hours and then made acidic to Congo Red at 35°to 40° C. with a diluted hydrochloric acid to precipitate a dye whichwas then filtered. The filtered dye cake was refined by dissolving it inwater to make up to 1500 parts of total volume and making the solutionacidic to Congo Red with hydrochloric acid to reprecipitate the dye. Thefiltered dye wet cake was again suspended in water, and the suspensionwas adjusted to 7 to 7.5 of pH. Then a solution of 18.5 parts ofcyanuric chloride in 100 parts of acetone was added dropwise thereto at0° to 5° C., and the mixture was stirred for 2 hours, salted out andfiltered. One half the phthalocyanine dye wet cake thus obtained and 130parts of sodium salt of 4-[5"-(4'"-,6'"-dichlorotriazin-2'"-yl)amino-2"-sulfophenylazo]-1-(3'-sulfophenyl)-3-methyl-pyrazolone(5)were dissolved in 2000 parts of water, and then a solution of 9.5 partsof diethylenetriamine in 100 parts of water was added thereto. Themixture was heated to 40° to 45° C. and stirred at this temperature for3 hours. After the reaction was completed, the reaction solution wasadjusted to 6.5 of pH and salted out to precipitate the desired dyewhich was then filtered and dried.

EXAMPLE 14

When the dye which was used in Example 12 was replaced by 1 part of thedye obtained by the following process, brilliant blue dyeings ofexcellent fastness were obtained.

The crude copper phthalocyanine sulfochloride wet cake which had beenobtained in Example 10 was slurried by thoroughly mixing with 300 partsof ice. The slurry was adjusted, at 0° to 3° C., to 6.5 to 7.0 of pHwith a diluted caustic soda solution. Then the neutralized slurry wasmixed with 2.5 parts by volume of a solution of 20 parts of calcinedsodium carbonate in 100 parts of water. After stirring for a short time,the mixture was immediately added to the primary condensation reactionmass prepared from 0.1 mole of cyanuric chloride and 0.02 mole oftetraethylenepentamine in 1200 parts of water. The whole was heated to40° to 45° C. and kept at this temperature for 3 hours while stirring.After the reaction was completed, the solution was adjusted to near 6.5of pH and salted out to precipitate the desired dye.

EXAMPLE 15

A solution of 18.5 parts of cyanuric chloride in 100 parts of acetonewas poured into 500 parts of ice water to obtain an aqueous suspensionof cyanuric chloride. To the suspension thus obtained was added, atbelow 5° C. over 1 hour, the solution of 34.1 parts of8-amino-1-naphthol-3,6-disulfonic acid monosodium salt in 400 parts ofwater which had been made slightly alkaline with 2 N-aqueous causticsoda. The mixture was kept at the same temperature for 2 hours and thenadjusted to 6 to 7 of pH with 2 N-aqueous sodium carbonate to completethe condensation reaction.

Thereafter a solution of 5.2 parts of diethylenetriamine in 50 parts ofwater was added thereto, and the mixture was kept at 35° to 40° C. for 3hours. After the second condensation was completed, the reactionsolution was cooled to below 5° C. and coupled with a diazo compoundobtained from 22.0 parts of 2-naphthylamine-1-sulfonic acid. Thesolution was adjusted to about 6.5 of pH and salted out with sodiumchloride to precipitate the desired monoazodye which was then filteredand dried at 40° to 50° C.

The dye thus obtained gave brilliant bluish red dyeings of good fastnessto sunlight in the same manner as described in Example 1.

EXAMPLE 16

A solution of 18.5 parts of cyanuric chloride in 100 parts in acetonewas poured into 500 parts of ice water to obtain an aqueous suspensionof cyanuric chloride. To the suspension was added a solution of 5.2parts of diethylenetriamine in 50 parts of water and the mixture wasstirred for 3 hours. Then a solution of 18.8 parts of2,4-diaminobenzene-1-sulfonic acid in 300 parts of water was addedthereto, and the mixture was heated to 30° to 35° C. and allowed toreact at the same temperature while keeping pH at 6 to 7 with 2N-aqueous sodium carbonate. After the condensation was completed, thesolution was cooled to below 5° C., diazotised by well-known methods andcoupled with 1-(2',5'-disulfophenyl)-3-methylpyrazolone. The reactionsolution was adjusted to about 6.5 of pH and salted out with sodiumchloride to precipitate the desired dye which was filtered and dried.

The dye thus obtained gave deep greenish yellow dyeings of good fastnessto sunlight in the same manner as described in Example 2.

EXAMPLE 17

100 parts of bleached plain weave cotton fabric was padded at roomtemperature with a 1% aqueous sodium carbonate solution, squeezed to200% of pick-up between rollers and dried at 100° C. Then the fabric waspadded with a 2% aqueous solution of the dye obtained in Example 2,squeezed to 200% of pick-up and then steamed at 110° C. for 5 minutes.The dyed fabric was thoroughly rinsed in water and then in a dilutesodium bicarbonate solution, soaped at the boil, rinsed and finallydried. The fabric was dyed in a deep orange shade which was fast towashing and sunlight.

EXAMPLE 18

100 parts of bleached plain weave cotton fabric was padded at roomtemperature with a dye liquor containing 1% of sodium bicarbonate, 0.2%of a highly sulfonated oil and 2% of the dye obtained in Example 4,squeezed between rollers to 200% of pick-up. After dried in a hot fluedrier, the fabric was rinsed successively in water and boiling soapsolution, rinsed and finally dried. The fabric was dyed in a deep blueshade which was fast to washing and sunlight.

EXAMPLE 19

100 parts of bleached plain weave cotton fabric was added at roomtemperature with a 1% aqueous sodium carbonate solution, squeezed to200% of pick-up between rollers and dried at 100° C. The fabric was thenpadded with a 2% aqueous solution of the dye obtained in Example 6,squeezed to 200% of pick-up between rollers and steamed at 100° C. for 5minutes. The dyed fabric was thoroughly rinsed successively in water anda dilute sodium bicarbonate solution, soaped at the boil, rinsed andfinally dried. The fabric was dyed in a deep blue shade which was fastto washing and sunlight.

EXAMPLE 20

A solution of 6.1 parts of disodium6-(4",6"-dichlorotriazin-2"-yl)amino-2-(2'-sulfophenylazo)-1-naphtholsulfonate(hereinafter referred to as dye 1) in 100 parts of water was mixed witha solution of 1.9 parts of tetraethylenepentamine in 30 parts of water,which amine solution had been adjusted to pH 5, and the mixture wasallowed to react at 25° to 30° C. at pH 3 to 5. After the reaction wasover, a solution of 6.4 parts of disodium4-[4"-(4'",6'"-dichlorotriazin-2-yl)amino-2"-sulfophenylazo]-1-(3'-sulfophenyl)-3-methyl-pyrazolone(hereinafter referred to as dye 2) in 100 parts of water was added tothe above reaction mixture, and the mixture was allowed to react at 30°to 35° C. at pH 5 to 6. After the reaction was over, a solution of 27.9parts of a 1:1 copper complex of trisodium6-(4'",6'"-dichlorotriazin-2'"-yl)amino-2-[4'-(2",5"-disulfophenylazo)-2'-oxy-5'-methylphenylazo]-1-naphthol-3-sulfonate(hereinafter referred to as dye 3) was further added to the abovereaction mixture, and the mixture was allowed to react at 40° to 45° C.,while the pH being kept at 6 to 7, if necessary, using a 2 N-sodiumcarbonate solution. After the reaction was over, the resulting solutionwas adjusted to pH 6.5 (This reaction mixture is hereinafter referred toas a dye liquor 1).

On the other hand, to a solution of 12.8 parts of the said dye 2 in 200parts of water was added a solution of 1.9 parts oftetraethylenepentamine in 30 parts of water, and the mixture was allowedto react at 30° to 35° C. for about 3 hours. After the reaction wasover, a solution of 27.9 parts of the said dye 3 in 300 parts of waterwas added to the above reaction mixture, and the mixture was allowed toreact at 40° to 45° C. for 10 to 12 hours, while the pH being kept at 6to 7, if desired, using a 2 N-sodium carbonate solution. After thereaction mixture was adjusted to pH 6.5 (This reaction mixture ishereinafter referred to as a dye liquor 2).

A mixture of the said dye liquor 1 and dye liquor 2 was spray-dried. Theresulting dye was used according to the same way as in Example 3 toobtain a dark black dyeing with good light fastness.

EXAMPLE 21

A solution of 6.1 parts of disodium6-(4",6"-dichlorotriazin-2"-yl)amino-2-(2'-sulfophenylazo)-1-naphthol-3-sulfonate,which solution had been adjusted to pH about 5, was added over about 30minutes to a solution of 2.4 parts of pentaethylenehexamine in 30 partsof water, which amine solution was kept at 25° to 30° C. and pH about 5using hydrochloric acid. The reaction mixture was kept at saidtemperature for about 3 hours while being kept at pH 3 to 5.Successively, a solution of 6.1 parts of1-(4',6'-dichlorotriazin-2'-yl)amino-3-methyl-4-(4",8"-disulfonaphthyl-2"-azo)benzenein 100 parts of water was added to the above reaction mixture, and themixture was allowed to react at 30° to 35° C. for about 5 hours whilebeing kept at pH 5 to 6. After the reaction was over, a solution of a1:1 copper complex of trisodium6-(4'",6'"-dichlorotriazin-2'"-yl)amino-2-[4'-(2",5"-disulfophenylazo)-2'-oxy-5'-methylphenylazo]-1-naphthol-3-sulfonatewas further added to the above reaction mixture, and the mixture wasallowed to react at 40° to 45° C. for 10 to 12 hours while being kept atpH 6 to 7. After the reaction was over, the resulting reaction mixturewas adjusted to pH 6.5 and spray-dried.

The dye obtained was used according to the same manner as in Example 3to obtain a dark greenish black dyeing with good light fastness.

What is claimed is:
 1. A compound of the formula ##STR63## wherein R andR' each are hydrogen, C₁ -C₄ alkyl or C₁ -C₄ hydroxyalkyl,m is aninteger from 1 to 6, n and n' are each an integer from 2 to 4, and whenm is 2 or more, n may be the same or different between 2 and 4, X ishydrogen or a group of the formula ##STR64## Y is hydrogen or a group ofthe formula ##STR65## and Z is hydrogen or a group of the formula##STR66## wherein R₁, R₁ ', and R₁ " each are hydrogen or C₁ -C₄ alkyl,R₂, R₂ ', and R₂ " each are halogen, and Q, Q', and Q" each are dyeresidues and are independently one member selected from the groupconsisting of members of the formulae as a free acid form ##STR67##wherein R₄ is hydrogen or C₁ -C₄ alkyl,V is halogen or methyl, l and qare each 0, 1, or 2 and s is 0, 1, or 3 with the proviso that X, Y, andZ are not hydrogen at the same time.